CN108473903A

CN108473903A - With poly- (methyl) acrylate copolymer of branched C17 alkyl chains and its purposes in lubricant oil composite

Info

Publication number: CN108473903A
Application number: CN201780006513.5A
Authority: CN
Inventors: S·奇霍尼; M·E·戴利; P·拉巴特; R·J·芬顿
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-01-13
Filing date: 2017-01-04
Publication date: 2018-08-31
Also published as: JP2019503421A; RU2729517C2; AU2017206531B2; JP6949032B2; RU2018129190A3; US10975325B2; EP3192857A1; WO2017121667A1; RU2018129190A; ES2847699T3; EP3402865A1; US20190016987A1; PL3402865T3; AU2017206531A1; ZA201805293B; EP3402865B1; BR112018014134A2

Abstract

The present invention relates to poly- (methyl) acrylate copolymers comprising (methyl) alkyl acrylate comonomer with branched C17 alkyl.The invention further relates to the lubricant oil composites for improving component as viscosity index (VI) comprising poly- (methyl) acrylate copolymer for containing (methyl) alkyl acrylate comonomer with branched C17 alkyl.

Description

It poly- (methyl) acrylate copolymer with branched C17 alkyl chains and its is lubricating Purposes in fluid composition

The present invention relates to poly- (methyl) third for including (methyl) alkyl acrylate comonomer with branched C17 alkyl Olefin(e) acid ester copolymer.The invention further relates to comprising containing (methyl) alkyl acrylate comonomer with branched C17 alkyl Poly- (methyl) acrylate copolymer as viscosity index (VI) improve component lubricant oil composite.

Known poly- (methyl) acrylate (PMA) is as the excellent viscosity index improver in multigrade lubricating oil (L.R.Rudnick (editor) Lubricant Additives, Chemistry and Applications, CRC Press, Taylor＆Francis Group, LLC, the second edition, 2009,315-338).

PMA is typically represented by two or three comonomer units：Methyl-prop with short, long and final medium alkyl chain The linear copolymer that olefin(e) acid ester is formed.Molecular weight is changed by 25,000g/mol to 500,000g/mol, but is existed due to high shear Under chain fracture the problem of making the shear stability of polymer drastically decline with the increase of molecular weight.

Shear stability can be branched by the improvement topological structure of polymer architecture such as pectination or star structure or introducing Alkyl chain and improve.Term branched the case where being also commonly used for star or comb-shaped polymer.

2010/0190671 A1 of US 8067349 B2 and US describes the comb-shaped polymer knot built by macromonomer Structure.These macromonomers are made of polyisobutene or hydrogenated butadiene polymer.

8513172 B2 of US describe poly- (methyl) third made of the single-stranded coupling generated controlled free radical polymerization The star polymer of olefin(e) acid ester.

Branched structure in star or comb-shaped polymer is made of linear polymer chain.Due to hypoergia reagent and big point Sub- monomer, the yield in the coupling reaction of star polymer and the incorporation macromonomer in comb-shaped polymer It is difficult to complete.

By using (methyl) acrylate monomer with branched alkyl chain, can more simply draw on a molecular scale Enter branch.Term (methyl) acrylate use herein includes methacrylate and acrylate derivative.

US 6746993 is described comprising (methyl) alkyl acrylate comonomer with branched C16-C36 alkyl Viscosity index improver.The each alkyl side chain of branched monomer includes a branch.The 2- decyl tetradecanes are referred to as preferred monomers Methyl acrylate and acrylate.

2014015584 A and JP 2014136772A of JP are described comprising (methyl) with branched C16-C36 alkyl The viscosity index improver of alkyl acrylate comonomer.Including the correspondent composition of viscosity index improver shows improvement Shear stability.

2014/017553 A1 of WO are described comprising (methyl) acrylic acid alkyl with straight chain or branched C1-C36 alkyl The viscosity index improver of ester comonomer.

These alkyl chains for being 1 using number of branches (branching number).It includes one that this, which means alkyl chain only, A tertiary CH structure divisions for leading to branch.Although known poly- (methyl) acrylate has higher branch number, they are being lubricated Purposes and effect in agent is unclear.

2009/124979 A1 of WO describe the synthetic method of the alcohol mixture with branched C17 alkyl.

Macromol.Chem.Phys.2014,215,1192 describe polymethacrylates and polyacrylate homopolymerization The polymerization of object and characterization.

To be with high molecular weight and the PMA of extraordinary viscosity index improver performance and the shear stability of enhancing It is beneficial, since it is desired that less material reaches the requirement in regulation.

The present invention provides high-molecular-weight poly (methyl) acrylate copolymer with high shear stability.The present invention is poly- (methyl) acrylate copolymer is formed by branched C17 methacrylate co-monomers unit.Although branch only includes to exist Short side Alliyl moieties in opposite long alkyl chain, and therefore it is not expected that should include branched C17 methacrylates Poly- (methyl) acrylate copolymer of comonomer unit has higher shear stability, but surprisingly significantly improves The shear stability of poly- (methyl) acrylate copolymer of the present invention.In addition, by non-thread with branched C17 methacrylates The viscosity index (VI) of preparaton made of the polymer of property analog improves the viscosity index (VI) of preparaton.

The viscosity of polymers compositions depends on molecular weight in inorganic or synthetic lubricant fluid preparaton.For example, usually by carrying The molecular weight of high polymer component and improve viscosity index (VI).On the other hand, there is higher molecular weight shear stability to reduce Disadvantage.Therefore, it is intended that preparing the viscosity index (VI) that can improve lubricant oil composite, while also obtaining the poly- of excellent shear stability Polymer component.

Can be lubricating oil at low temperatures and high temperatures the purpose of the present invention is preparing poly- (methyl) acrylate copolymer Composition provides advantageous rheology and improves performance (including high viscosity index (HVI) and excellent shear stability).

The purpose passes through the branched C17 Arrcostabs (C17MA) of copolymerization (methyl) acrylic acid and selected straight chain or branched total Polycondensation monomer is realized.

Therefore, in one embodiment, the present invention relates to poly- (methyl) acrylate copolymers, can be wrapped by polymerizeing Mixture containing following substance and obtain

(A) (methyl) acrylic acid C17 Arrcostabs, wherein C17 alkyl chains are with average branchiness (isotactic index (iso- Index it is)) 2.0-4.0, preferably 2.8-3.7 is branched,

(B) methyl methacrylate and/or methyl acrylate, and

(C) alkyl methacrylate and/or alkyl acrylate with straight chain or branched C2-30 alkyl chains.

In a preferred embodiment of the invention, the weight average molecular weight M of copolymer_WIt is measured according to DIN 55672-1 For 10,000-800,000g/mol, preferably 100,000-750,000g/mol, more preferable 300,000-700,000g/mol, most It is preferred that 300,000-700,000g/mol.

In another preferred embodiment of the present invention, it is based on the total weight of poly- (methyl) acrylate copolymer, copolymerization The amount of monomer (A) is 10-80 weight %, preferably 25-60 weight %, more preferable 30-50 weight %, most preferably 35-45 weight %.

In another preferred embodiment of the present invention, it is based on the total weight of poly- (methyl) acrylate copolymer, copolymerization The amount of monomer (B) is 5-40 weight %, preferably 10-35 weight %, more preferable 15-35 weight %, most preferably 15-30 weight %.

In another preferred embodiment of the present invention, it is based on the total weight of poly- (methyl) acrylate copolymer, copolymerization The amount of monomer (C) is 15-80 weight %, preferably 25-70 weight %, more preferable 30-70 weight %, most preferably 35-70 weight %.

In another preferred embodiment of the present invention, comonomer (C) is with straight chain or branched C2-C30 alkyl chains Alkyl methacrylate and/or alkyl acrylate, the average branchiness of the alkyl chain is 1.0, selected from ethyl, just Propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, hexyl, heptyl, octyl, 2- ethylhexyls, 2- propyl Heptyl, nonyl, decyl, stearyl, lauryl, octadecyl, heptadecyl, nonadecyl, eicosyl, heneicosyl, Docosyl, tricosyl, tetracosyl, pentacosyl, cerul, heptacosane base, octacosyl, Nonacosyl, melissyl He Shan Yu bases.

Another embodiment of the present invention is related to a kind of concentrate composition for lubricating oil, it includes：

(i) diluent, and

(ii) poly- (methyl) acrylate copolymer of the present invention of 30-70 weight %.

Another embodiment of the present invention is related to a kind of lubricant oil composite, it includes：

(a) base oil,

(b) poly- (methyl) acrylate copolymer of the invention, and

(c) additive.

Another embodiment of the present invention is related to a kind of lubricant oil composite, it includes

Poly- (methyl) acrylate copolymer as herein defined of -0.1-30 weight %,

The base oil of -70-99.9 weight %, and

The additive of -0.05-20 weight %,

It is highly preferred that

Poly- (methyl) acrylate copolymer of -0.5-25.0 weight %,

The base oil of -75-99.0 weight %, and

The additive of -0.1-15 weight %；

Even further preferably,

Poly- (methyl) acrylate copolymer of -1.0-15.0 weight %,

The base oil of -80.0-95.0 weight %, and

The additive of -0.5-15.0 weight %；

Most preferably,

Poly- (methyl) acrylate copolymer of -1.5-10.0 weight %,

The base oil of -85.0-90.0 weight %, and

The additive of -1.0-15.0 weight %；

In particular,

Poly- (methyl) acrylate copolymer of -2.0-7.0 weight %,

The base oil of -85.0-90.0 weight %, and

The additive of -5.0-15.0 weight %.

In another preferred embodiment of lubricant oil composite, the composition include it is at least one selected from antioxidant, It is oxidation retarder, corrosion inhibitor, friction modifiers, matal deactivator, antirust agent, antifoaming agent, viscosity index (VI) reinforcing agent, additional The additive of pour-point depressant, dispersant, detergent, extreme pressure agent and/or antiwear additive.

In another preferred embodiment of lubricant oil composite, the composition is with according to ASTM D7109, (30 logical Journey) it measures and is calculated less than 50, preferably smaller than 48 by ASTM D6022, more preferable 41-47, even more preferably 42-46's cuts Cut stability index.

In another preferred embodiment of lubricant oil composite, high temperature high shear movement of the composition at 100 DEG C According to ASTM D5481, (porous capillary (Multicell Capillary) is measured as at least 4.00 to 6.00mPas to viscosity, excellent Choosing at least 4.50 to 5.85mPas, more preferably at least 5.00 to 5.75mPas, even more desirably at least 5.20 to 5.70mPas, most Preferably at least 5.40 to 5.65mPas, the high-temperature high shear viscosity at 150 DEG C is surveyed according to ASTM D5481 (porous capillary) Amount is 2.50-2.70mPas, preferably 2.55-2.65mPas.

In another preferred embodiment of lubricant oil composite, the viscosity index (VI) (VI) of the composition is according to ASTM D2270 is measured as at least 180, preferably at least 190, more preferably at least 200, even more preferably 205-220, most preferably 208-215.

Another embodiment of the present invention be related to lubricant oil composite automatic transmission fluids, manual transmission fluid, Purposes in hydraulic fluid, lubricating grease, gear fluids, metal working fluids, crankcase engine oil or shock absorber fluids.

Another embodiment of the present invention is related to a kind of method for improving the shear stability of lubricant oil composite, Described in method include the steps that poly- (methyl) acrylate copolymer of the present invention is added into base oil and optional additive.

Poly- (methyl) acrylate copolymer of the present invention includes comonomer (A), is (methyl) acrylic acid C17 alkyl Ester.(methyl) acrylic acid C17 Arrcostabs are preferably the branched alkyl ester of (methyl) acrylic acid.

Comonomer (A) is to be based on the total weight of poly- (methyl) acrylate copolymer of the present invention for 5-80 weight %, more It is preferred that the amount of 8-70 weight %, even more preferably 8-60 weight %, most preferably 8-50 weight %, especially 9-50 weight % exist In poly- (methyl) acrylate copolymer of the present invention.

The average branchiness (isotactic index) of C17 alkyl chains in (methyl) acrylic acid C17 Arrcostabs comonomer (A) is 2.0-4.0, preferably 2.8-3.7, more preferable 2.9-3.6, even more preferably 3.0-3.5, most preferably 3.05-3.40, especially 3.08-3.20。

The average branchiness (isotactic index) of (methyl) acrylic acid C17 Arrcostabs is required for the present invention, because not Too high average branchiness is for (methyl) acrylic acid C17 Arrcostabs as comonomer (A) in poly- (methyl) propylene of the present invention The purposes that purposes and these copolymers in acid ester copolymer change rheological characteristic in lubricant oil composite is important.

In the context of the present invention, the methyl number that average branchiness is commonly defined as in alcohol molecule subtracts 1.Average branch Degree is the assembly average of the degree of branching of sample molecule.

Average branchiness can pass through¹H-NMR spectrum measure as follows：For this purpose, first by alcohol or alcohol mixture (such as C17 alcohol Or C17 alcohol mixtures) sample it is derivative with trichloroacetyl isocyanate (TAI).This converts C17 alcohol to carbamate.

The signal for the primary alconol being esterified in this way is located at δ=4.7-4.0ppm, esterification secondary alcohol (if present) Signal is located at 5ppm, and water present in sample reacts with TAI and generates carbamic acid.All methyl, methylene and secondary first Matrix is located at the range of 2.4-0.4pm.Signal<1ppm belongs to methyl.By the spectrum so obtained, can calculate as follows Average branchiness (isotactic index)：

Isotactic index=((F (CH₃)/3)/(F(CH₂OH)/2))-1

Wherein F (CH₃) correspond to the signal area of methyl proton, F (CH₂OH) it is CH₂OH group methylene protons Signal area.

The C17 alcohol mixtures for being used to prepare (methyl) acrylic acid C17 Arrcostabs of the invention preferably have based on the mixing of C17 alcohol The total weight of object is at least 95 weight %, more preferably at least 98 weight %, and especially at least 99 weight %'s has 17 carbon originals The alcohol content of son.C17 alcohol mixtures especially substantially (are more than 99.5 weight %, particular more than the journey of 99.9 weight % Degree) mixture that is made of the alcohol with 17 carbon atoms.

In order to prepare such C17 alcohol mixture, 2011/064190 A1 of WO 2009/124979 A1 and WO is referred to herein And document cited therein.These applications are incorporated herein by reference, especially with regard to prepare branched C17 alcohol and measure these The method of average branchiness in molecule.

2011/064190 A1 of WO, which are further disclosed, converts branched C17 alcohol to corresponding (methyl) acrylic acid C17 alkane Base ester.2011/064190 A1 of WO are used to obtain these programs of the branched C17 Arrcostabs of (methyl) acrylic acid also by reference simultaneously Enter herein.

C17 alcohol mixtures have the average branchiness of at least high-purity and 2.8-3.7 of 95 weight %.Therefore, (first is prepared Base) acrylate the method for the present invention therefore same (methyl) acrylic acid C17 Arrcostabs that high-purity is provided.It so far can city (methyl) acrylic acid C17 Arrcostabs bought are typically the mixture of (methyl) acrylic acid C16 and C18 Arrcostab.Therefore, no With in batch of material mixing and isomer proportion may be different.So far, this has the performance of gained (co) polymer unfavorable It influences.

Therefore, particularly advantageous characteristics is by according to WO 2009/124979 A1 and WO 2011/ within a context The low-freezing of (methyl) acrylate of C17 alcohol mixtures prepared by the method for 064190 A1.Due to the high-purity and constant The degree of branching, solidification point is preferably shorter than 0 DEG C, more preferably less than -20 DEG C, even more preferably less than -40 DEG C (under atmospheric pressure).

It is further advantageous that according to the method for 2011/064190 A1 of WO 2009/124979 A1 and WO, because obtaining High esterification degree and realize high yield.It is formed in addition, significant polymer does not occur in esterification or last handling process, and And final product is essentially colorless.

The comonomer (B) of poly- (methyl) acrylate copolymer of the present invention is (methyl) methyl acrylate comonomer. I.e. comonomer (B) is or mixtures thereof methyl methacrylate or methyl acrylate.

Comonomer (B) is to be based on the total weight of poly- (methyl) acrylate copolymer of the present invention for 5-40 weight %, more It is preferred that 10-35 weight %, even more preferably 15-35 weight %, the amount of most preferably 20-35 weight % is present in the poly- (first of the present invention Base) in acrylate copolymer.

The comonomer (C) of poly- (methyl) acrylate copolymer of the present invention, which is selected from, has straight chain or branched C2-C30 alkyl Chain, preferably straight chain or branched C2-C22 alkyl chains, or the more preferably methacrylic acid of straight chain or branched C2-C18 alkyl chains Arrcostab and/or alkyl acrylate.

Comonomer (C) can be preferably with straight chain or branched C2-C30 alkyl chains and such as undefined straight chain or branch Change straight chain, cross-linking type or the branching comonomer of C2-C30 alkyl chains.It is highly preferred that comonomer (C) is straight chain or branched (degree of branching 1.0).

Cross-linking type comonomer is a kind of multifunctional comonomer, it can form crosslinking when being covalently attached polymer chain Copolymer.

Comonomer (C) is usually the alkyl methacrylate and/or third with straight chain or branched C2-C30 alkyl chains Olefin(e) acid Arrcostab, wherein straight chain or branched C2-C30 alkyl chains have 1.0 average branchiness, and wherein C2-C30 alkyl chains Selected from ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, hexyl, heptyl, octyl, 2- ethyls Hexyl, 2- propylheptyls, nonyl, decyl, stearyl, lauryl, octadecyl, heptadecyl, nonadecyl, eicosyl, Heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, cerul, cerul, Octacosyl, nonacosyl, melissyl He Shan Yu bases.

That be especially preferred as comonomer (C) is stearyl and/or lauryl (methyl) acrylate co-monomers, spy It is not in the case where comonomer (B) is methyl methacrylate and/or methyl acrylate.

Comonomer (C) is to be based on the total weight of poly- (methyl) acrylate copolymer of the present invention for 20-80 weight %, more It is preferred that 25-70 weight %, even more preferably 30-70 weight %, the amount of most preferably 35-70 weight % is present in the poly- (first of the present invention Base) in acrylate copolymer.

In another highly preferred embodiment of the present invention, poly- (methyl) acrylate copolymer of the present invention preferably wraps The comonomer (A) of the amount of the % of weight containing 5-80, the comonomer (B) of the amount of 5-40 weight % and the amount of 20-80 weight % Comonomer (C).

In another highly preferred embodiment of the present invention, poly- (methyl) acrylate copolymer of the present invention preferably wraps The comonomer (A) of the amount of the % of weight containing 8-70, the comonomer (B) of the amount of 10-35 weight % and the amount of 30-70 weight % Comonomer (C).

In the another highly preferred embodiment of the present invention, poly- (methyl) acrylate copolymer of the present invention preferably wraps The comonomer (A) of the amount of the % of weight containing 8-60, the comonomer (B) of the amount of 15-35 weight % and the amount of 35-70 weight % Comonomer (C).

Use (methyl) acrylate monomer of hydroxyl, epoxy group and/or amino-functional and other functional modified (first Base) acrylate monomer is generally also possible, but do not have more preferably other functional groups (such as hydroxyl, epoxy group and/or Amido functional group etc.) pure acrylic acid Arrcostab as comonomer (A), (B) and (C).

Optionally, other than basic comonomer (A), (B) and (C), as other comonomers, at most 50 weights Measure %, preferably up to 20 weight %, more preferably up to 10 weight %, even more preferably at most 5 weight %, most preferably up to 2 weights The following monomer of amount % listed by way of example can be used for poly- (methyl) acrylate copolymer of the present invention：Aromatic vinyl Compound, such as styrene, α-methylstyrene, vinyltoluene or to (tertiary butyl) styrene；Acrylic acid and metering system Acid；Acrylamide and Methacrylamide；Maleic acid and its acid imide and C1-C10 Arrcostabs；Fumaric acid and its acid imide and C1-C10 Arrcostabs；Itaconic acid and its acid imide and its C1-C10 Arrcostabs；Acrylonitrile and methacrylonitrile.

On the other hand, for other comonomers are not present other than comonomer (A), (B) and (C), more preferably originally Poly- (methyl) acrylate copolymer is invented only to be made of comonomer (A), (B) and (C).

The molecular weight distribution measured by using the gpc analysis of polystyrene standards is preferably smaller than 5.0, usually 2.0- 4.5, preferably 3.0-4.4, more preferable 3.1-4.3.

Molecular weight is measured by using the GPC of polymethyl methacrylate standard specimen.Therefore the average molecular weight measured is opposite It is not absolute for standard.

The conventional method of free radical polymerization can be used for preparing poly- (methyl) acrylate copolymer of the present invention.Corresponding methyl-prop The polymerization of olefin(e) acid alkyl ester monomer can under various conditions, including bulk polymerization, polymerisation in solution are (excellent usually in organic solvent Select in mineral oil) it carries out.

In polymerisation in solution, reaction mixture includes diluent, (methyl) alkyl acrylate monomer to be polymerized, polymerization Initiator and common chain-transferring agent and optional crosslinking agent.

Diluent can be any unreactive hydrocarbons.The concentration of total monomer can be in the range of 30-90%.It is used herein " total Monomer addition " refers to the combined amount of all monomers in initial (i.e. unreacted) reaction mixture.

When preparing poly- (methyl) acrylate copolymer of the invention by free radical polymerization, alkyl methacrylate list Body can simultaneously or sequentially polymerize, or can with the time will monomer feed reactor in.For example, can be by (methyl) acrylic acid The blend of C1, C2-C30 (preferably C2-C18) alkyl ester monomer and the branched C17 alkyl ester monomers component of (methyl) acrylic acid with The time feeds together with initiator feed in reaction vessel.

Suitable polymerization initiator includes the initiator dissociated when heated to generate free radicals, such as peroxide chemical combination Object such as benzoyl peroxide base, t-butyl perbenzoate, tert-butyl peroctoate and cumene hydroperoxide；And azo-compound is such as Azo isobutyronitrile and 2,2'- azos two (2- methylbutyronitriles).Mixture includes 0.001-5.0 weights relative to total monomer mixture Measure the initiator of %.For example, it is contemplated that 0.02-4.0 weight %, 0.02-3.5 weight %.Usually using 0.02-2.0 weight %.

Suitable chain-transferring agent includes those of this field routine, such as mercaptan and alcohol.For example, tridecyl mercaptan, ten Dialkyl group mercaptan and ethanethio and bifunctional mercaptan such as hexanedithiol may be used as chain-transferring agent.Chain tra nsfer ready for use The required shear stability of required molecular weight and polymer of the selection of the amount of agent based on polymer to be synthesized is horizontal, i.e., such as Fruiting period hopes the polymer for relatively having shear stable, then more chain-transferring agent can be added in reaction mixture.Chain-transferring agent phase Monomer mixture is added with the amount of 0.001-3 weight % in reaction mixture or monomer feed.

By way of example and not limitation, all components the reaction equipped with blender, thermometer and reflux condenser is packed into hold In device, and it is heated to 50-125 DEG C of temperature under stiring under nitrogen protection and is kept for 0.5-15 hours polymerize instead It answers.

Obtain viscous solution product as the above method of the present copolymer in diluent.

The invention further relates to the concentrate compositions of poly- (methyl) acrylate copolymer of the present invention.

Concentrate composition is preferably intended in lubricating oil.Concentrate composition can be by being added at least one dilution Agent, and diluted optionally by other additives are added, lubricating oil composition is thus obtained by concentrate composition of the present invention Object.A kind of preferred diluent is base oil.

Amount of poly- (methyl) acrylate copolymer in concentrate composition is typically based on the gross weight of concentrate composition Amount is 20-95 weight %, preferably 25-85 weight %, more preferable 30-75 weight %, most preferably 30-70 weight %.

Therefore, in order to form lubricating oil of the present invention, by base oil in a usual manner (i.e. by providing poly- (methyl) of the invention Acrylate copolymer and be added into the base oil with other optional additives) and with poly- (methyl) propylene of the present invention Acid ester copolymer processing or mixing, to provide the lubricant oil composite with required technical specification and required concentration of component.

In an especially preferred embodiment, poly- (methyl) acrylate copolymer of the present invention is being diluted with copolymer Opposite concentrated solution form in agent is added in base oil.Flux oil can be the following any oil for being suitable as base oil.

The invention further relates to the lubricant oil composites for including poly- (methyl) acrylic acid ester copolymer composition of the present invention.

Lubricant oil composite includes following components：

(a) at least one base oil component,

(b) poly- (methyl) acrylate copolymer as herein defined, and

(c) other additives.

Poly- (methyl) acrylate copolymer of the present invention, base oil component and optional additive are in lubricant oil composite Amount be generally as follows：

In most general embodiment, poly- (methyl) acrylate copolymer, the 70-99.9 for 0.1-30 weight % are measured The additive of the base oil and 0.05-10 weight % of weight %.

Preferably, the basis of poly- (methyl) acrylate copolymer for 0.5-25.0 weight %, 75-99.0 weight % are measured The additive of oil and 0.1-20 weight %.

It is highly preferred that amount is poly- (methyl) acrylate copolymer of 1.0-15.0 weight %, 80.0-95.0 weight % The additive of base oil and 0.5-15.0 weight %.

Most preferably, poly- (methyl) acrylate copolymer for 1.5-10.0 weight %, 85.0-90.0 weight % are measured The additive of base oil and 0.8-15.0 weight %.

In lubricant oil composite of the present invention, the weight of base oil component and poly- (methyl) acrylate copolymer of the present invention Than being usually 10-1000, more preferable 20-500, even more preferably 25-200, most preferably 30-150.

In another preferred embodiment of the present invention, lubricant oil composite includes every 100 weight base fluids 0.1- The pure block copolymer of 10.0 parts by weight, preferably 0.2-5.0 parts by weight, more preferable 0.5-3.0 parts by weight (excludes diluent basis Oil).Certain preferred dose depends on base oil.

Lubricant oil composite of the present invention includes at least one additive, is preferably selected from antioxidant, oxidation retarder, corruption Corrosion inhibitor, matal deactivator, antirust agent, antifoaming agent, viscosity index (VI) reinforcing agent, additional pour-point depressant, divides friction modifiers Powder, detergent, other extreme pressure agents and/or antiwear additive.It is described in more detail below preferred additive.

Lubricant oil composite of the present invention is characterized in that (30 logical based on D7109 European Diesel Injector Journey) shear stability index and calculate the shear stability indexes (SSI) of lubricant compositions according to ASTM D6022 and survey The high shear stability of amount.It is calculated based on D7109 (30 logical journeys) and by the SSI of ASTM D6022, SSI of the invention is usual Less than 50, preferably smaller than 46, more preferably less than 42.

Additionally or alternatively, lubricant oil composite of the present invention is characterized in that through the HTHS at 100 DEG C and 150 DEG C So-called high temperature high shear (HTHS) viscosity stability of viscosity measurement.Lubricant oil composite of the present invention have according to ASTM The high-temperature high shear viscosity that D5481 (porous capillary) is measured at 100 DEG C is generally at least 4.00-6.00mPas, preferably extremely Few 4.50-5.85mPas, more preferably at least 5.00-5.75mPas, even more desirably at least 5.20-5.70mPas, most preferably extremely 5.40-5.65mPass and/or the high-temperature high shear viscosity according to ASTM D5481 (porous capillary) measurements at 150 DEG C less Usually 2.50-2.70mPas, preferably 2.55-2.65mPas.

Additionally or alternatively, lubricant oil composite of the present invention also shows that the high viscosity measured by ASTM D2270 refers to Number (VI).The preferred viscosities exponential quantity of lubricant oil composite of the present invention is at least 180, preferably at least 190, more preferably at least 200, Even more preferably 205-220, most preferably 208-215.

Additionally or alternatively, the processing speed of lubricant oil composite of the present invention preferably can be in some selected embodiment party It is 1.0-30.0 weight %, preferably 2.0-25.0 weight %, more preferable 2.5-15.0 weight %, most preferably 3.0-5.0 weight in case Measure %.

Finally, in addition to above-mentioned performance characteristic or alternatively, lubricant oil composite of the present invention is shown according to ASTM D445 The kinematic viscosity at 100 DEG C measured is 6.9-9.3mm²/ s (cSt), 7.2-9.2mm²/ s (cSt), more preferable 7.5- 9.1mm²/ s, even more preferably 7.8-9.0mm²/ s, most preferably 8.0-8.8mm²/s。

In short, lubricant oil composite provides excellent viscosity characteristics in low temperature and high temperature and while being subjected to shearing force.

The preferred base oil for being intended for lubricant oil composite of the present invention include mineral oil, poly-alpha-olefin synthetic oil and its Mixture.Suitable base oil further includes the oil base stock obtained by the isomerization of synthetic wax and slack wax, and is passed through It is hydrocracked the aromatics and polar compound and the oil base stock that generates of (rather than solvent extraction) crude oil.In general, mineral oil and synthesis Kinematic viscosity at each comfortable 100 DEG C of base oil is 1-40mm²/ s, but typically each oil of application requirement has at 100 DEG C 1-10mm²The viscosity of/s.

Mineral oil for use in the present invention includes all common mineral oil base stocks.This is included in chemical constitution For the oil of cycloalkane, alkane or aromatic compounds.The methylene that naphthenic oil is arranged by loop type forms, and is connected in middle ring Alkane side chain.Pour point is usually less than the pour point of paraffin oil.Paraffin oil includes the straight chain or branched hydrocarbon of saturation.High molecular weight it is straight Alkane improves the pour point of oil, and is usually removed by dewaxing.Aromatic oil is the closing carbon with half unsaturated characteristic The hydrocarbon of ring, and may have the side chain of connection.This oil is easier to degrade than paraffin oil and naphthenic oil, and leads to corrosivity pair Product.

In fact, oil base stock generally comprises a kind of Chemical composition that, it includes all three (alkane, cycloalkane and Aromatic hydrocarbon) a part.The discussion of type in relation to oil base stock, referring to Motor Oils and Engine Lubrication by A.Schilling, Scientific Publications, 1968,2.2-2.5 sections.

Poly- (methyl) acrylate copolymer can be used in the oil of alkane, cycloalkane and aromatic type.For example, poly- (methyl) acrylate copolymer can be used for I-V class base oils.These classes are well known to those skilled in the art.In addition, poly- (first Base) acrylate copolymer can be used in natural gas liquefaction (gas to liquid oil).

Natural gas liquefaction (GTL) is well known in the art.Gaseous source includes the material of wide scope, such as naturally Gas, methane, C1-C3 alkane, landfill gas etc..Such gas can pass through natural gas liquefaction (GTL) technique (such as United States Patent (USP) No.6, the technique described in 497,812) it is converted into the liquid hydrocarbon product withdrawn for being suitable as lubricating base oil, the disclosure of which passes through It is incorporated herein by reference.

Base oil (hereinafter referred to as " GTL base oils ") derived from gaseous source usually has the viscosity index (VI) more than 130, Less than the sulfur content of 0.3 weight %, including the saturated hydrocarbons (isoalkane) more than 90 weight %, usual 95-100 weight %'s is branched Aliphatic hydrocarbon has the pour point less than -15 DEG C to -20 DEG C.

GTL base oils can be with more conventional base oil as by being mixed with I-V classes as defined in API.For example, lubricant compositions Base oil component can include the GTL base oils of 1-100 weight %.

Therefore, lubricant oil composite can at least partly be derived from gaseous source and include poly- (methyl) acrylic acid of the present invention Ester copolymer is as pour-point depressant.

Oil can be refined by using acid, alkali and the conventional method of clay or other reagents such as aluminium chloride or they It can be the extraction for example by being prepared by for example phenol, sulfur dioxide, furfural, Dichlorodiethyl ether equal solvent extract with solvent Oil.Their hydrotreatings or hydrofinishing can be dewaxed, or be hydrocracked by cooling or CATALYTIC DEWAXING TECHNIQUE.Mineral Oil can be produced by natural crude oil source, or be made of the residue of isomerization wax material or other refining process.It is preferred to close It is the oligomer of alpha-olefin, the especially oligomer of 1- decene, also referred to as poly alpha olefin or PAO at oil.

Or mixtures thereof oil that base oil can derive autofining, re-refining.Unpurified oil, which is obtained directly from, naturally to be come Source or synthesis source (for example, coal, shale or tar sand bitumen), without being further purified or handling.The example of unrefined oil Including the shale oil directly obtained from distillation procedure, directly directly obtain from the petroleum oil that obtains of distillation or from esterification technique Ester oil, then it is not used respectively after further treatment.Refined oil is similar to unrefined oil, the difference is that refined Oil is handled in one or more purification steps to improve one or more performances.Suitable purification technique include distillation, Hydrotreating, dewaxing, solvent extraction, acid or alkali extraction, filtering and diafiltration, all these is known to those skilled in the art 's.Rerefined oils are obtained by by similar to used oil is handled in the refined oil technique of those for obtaining.These are heavy refined Oil is also referred to as oil recovery or reprocessed oils, and is usually additionally added by the technology for removing useless additive and oil decomposition product Work.

Optional conventional oil additive

It is possible that at least one additional conventional oil additive is added into lubricant oil composite of the present invention, but in each feelings It is not enforceable under condition.The lubricant compositions, such as lubricating grease, gear fluids, metal working fluids and hydraulic flow Body can include additionally other additives added to be further improved its basic performance.

Such additive includes：Other antioxidants or oxidation retarder, corrosion inhibitor, friction modifiers, metallic blunt Agent, antirust agent, antifoaming agent, viscosity index (VI) reinforcing agent, additional pour-point depressant, dispersant, detergent, other extreme pressure agents and/ Or antiwear additive.

Such additive exists for each in them with conventional amount used, and lubricating oil composition is based in each case The total weight of object is 0.01-10.0 weight %, preferably 0.05-3.0 weight %, more preferable 0.1-1.0 weight %.Other additives Example it is as follows：

1. the example of phenol antioxidant：

1.1. alkylation monophenols：2,6 di tert butyl 4 methyl phenol, 2- butyl -4,6- xylenols, bis- uncles of 2,6- Butyl -4- ethyl -phenols, 2,6- di-t-butyl -4- normal-butyls phenol, 2,6- di-t-butyl -4- isobutyl groups phenol, bis- rings of 2,6- Amyl -4- methylphenols, 2- (Alpha-Methyl cyclohexyl) -4,6- xylenols, (the octadecyl) -4- of 2,6- bis- methylphenols, 2,4,6- thricyclohexyls phenol, 2,6- di-t-butyl -4- methoxymetllyl-phenols, straight chain nonyl phenol or on side chain it is branched Nonyl phenol such as 2,6- dinonyl -4- methylphenols, 2,4- dimethyl -6- (1'- methylundecane -1'- bases)-phenol, 2,4- Dimethyl -6- (1'- methyl heptadecane -1'- bases)-phenol, 2,4- dimethyl -6- (1'- methyltridec -1'- bases)-phenol and Its mixture；

1.2. Alkyithiomethylphenols：2,4- dioctyl thiomethyl -6- tert-butyl phenols, 2,4- dioctyl thiomethyls -6- Methylphenol, 2,4- dioctyl thiomethyl -6- ethyl -phenols, the bis- dodecylthiomethyl -4- nonyl phenols of 2,6-；

1.3. quinhydrones and alkvlated hvdroquinones：2,6- di-t-butyl -4- metoxyphenols, DBH 2,5 di tert butylhydroquinone, 2,5- Two amyl hydroquinones, 2,6- diphenyl -4- octade-cyloxyphenols, 2,6- di-tert-butyl hydroquinones, 2,5- di-t-butyl -4- hydroxyls Anisole, 3,5- di-t-butyls -4-HA, 3,5- di-tert-butyl-hydroxy phenyls stearate, bis- (bis- uncles of 3,5- Butyl -4- hydroxy phenyls) adipate ester；

1.4. tocopherol：α-, β-, γ-or Delta-Tocopherol and its mixture (such as vitamin E)；

1.5. Hydroxylated thiodiphenyl ethers：2,2'- thio-bis- (6- tert-butyl-4-methyl-Phenols), 2,2'- are thio-bis- (4- octyl phenols), 4,4'- thio-bis- (6- tertiary butyl -3- methylphenols), thio-bis- (6- tertiary butyl -2- methylbenzenes of 4,4'- Phenol), 4,4'- thio-bis- (3,6- di-sec-amyls phenol), bis- (2,6- dimethyl -4- hydroxy-phenies) disulphide of 4,4'-；

1.6. alkylidene bisphenols：2,2'- methylene-bis- (6- tert-butyl-4-methyl-Phenols), 2,2'- methylene-bis- (6- Tertiary butyl -4- ethyl -phenols), 2,2'- methylene-bis- [4- methyl -6- (Alpha-Methyl cyclohexyl) phenol], 2,2'- methylene-bis- (4- methyl -6- cyclohexylphenols), 2,2'- methylene-bis- (6- nonyl -4- methylphenols), 2,2'- methylene-bis- (4,6- bis- Tert-butyl phenol), 2,2'- ethylidene-bis- (4,6- DI-tert-butylphenol compounds), 2,2'- ethylidene-bis- (6- tertiary butyl -4- isobutyl groups Phenol), 2,2'- methylene-bis- [6- (α-methylbenzyl) -4- nonyl phenols], 2,2'- methylene-bis- [6- (alpha, alpha-dimethyls Benzyl) -4- nonyl phenols], 4,4'- methylene-bis(2,6-di-butyl phenol), 4,4'- methylene-bis- (6- tertiary butyls -2- Methylphenol), bis- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) butane of 1,1-, the bis- (3- tertiary butyl -5- methyl -2- hydroxyls of 2,6- Base benzyl) -4- methylphenols, 1,1,3- tri- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) butane, bis- (the 5- tertiary butyls-of 1,1- 4- hydroxy-2-methyls phenyl) -3- dodecyl sulfydryls butane, the bis- [bis- (3'- tertiary butyl -4'- hydroxy benzenes of 3,3- of ethylene glycol Base) butyrate], bis- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) bicyclopentadiene, bis- [2- (3'- tertiary butyl -2'- hydroxyls - 5'- methylbenzyls) -6- tertiary butyl -4- aminomethyl phenyls] terephthalate, bis- (3,5- dimethyl -2- hydroxy phenyls) fourths of 1,1- Bis- (5- tertiary butyl-4-hydroxy -2- the aminomethyl phenyls) -4- of bis- (3,5- di-tert-butyl-hydroxy phenyls) propane of alkane, 2,2-, 2,2- Dodecyl sulfydryl butane, 1,1,5,5- tetra- (5- tertiary butyl-4-hydroxy -2- aminomethyl phenyls) pentane；

1.7.O-, N- and S- benzyl compounds：3,5,3', 5'- tetra-tert -4,4'- dihydroxy dibenzyl ether, octadecane Base -4- hydroxyls -3,5- dimethyl benzyls-mercaptoacetate, tridecyl -4- hydroxyl -3,5- di-t-butyl Benzylmercapto acetic acid Ester, three (3,5- di-tert-butyl-4-hydroxyl benzyls) amine, bis- (4- tertiary butyl -3- hydroxyl -2,6- dimethyl benzyls) two are thio to benzene Dicarboxylic acid esters, bis- (3,5- di-tert-butyl-4-hydroxyl benzyls) sulfide, iso-octyl -3,5- di-tert-butyl-4-hydroxyl benzyl sulfydryls Acetic acid esters；

1.8. Hvdroxvbenzvlated malonates：The double octadecanes of bis- (3,5- di-t-butyl -2- hydroxybenzyls) malonic acid of 2,2- Base ester, 2- (3- tertiary butyl-4-hydroxy -5- methylbenzyls) malonic acid double stearyl, the bis- (3,5- di-t-butyls -4- of 2,2- Hydroxybenzyl) the double didodecylmercaptoethyl ester of malonic acid, bis- (3,5- di-tert-butyl-4-hydroxyl benzyls) malonic acid two of 2,2- [4- (1,1,3,3- tetramethyls-butyl)-phenyl] ester；

1.9. Hydroxybenzyl aromatics：1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -2,4,6- trimethyls Bis- (3,5- the di-tert-butyl-4-hydroxyl benzyls) -2,3,5,6- durols of benzene, the 1,4-, (3,5- di-t-butyls -4- of 2,4,6- tri- Hydroxybenzyl) phenol.

1.10. triaizine compounds：Bis- octylmercapto-the 6- of 2,4- (3,5- di-t-butyl -4- hydroxy benzenes amido) -1,3,5- three Bis- (3,5- di-t-butyl -4- hydroxy benzenes the amido) -1,3,5- triazines of piperazine, 2- octylmercaptos -4,6-, 2- octyls-sulfydryl -4,6- are double (3,5- di-t-butyl -4- hydroxyphenoxies) -1,3,5- triazines, 2,4,6- tri- (3,5- di-t-butyl -4- hydroxyphenoxies) -1, 2,3- triazines, 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid ester, (4- tertiary butyl -3- hydroxyls of 1,3,5- tri- Base -2,6- dimethyl benzyls) isocyanuric acid ester, 2,4,6- tri- (3,5- di-t-butyl -4- leptodactylines) -1,3,5- triazines, 1,3,5- tri- (3,5- di-tert-butyl-hydroxy phenyls propiono) hexahydro -1,3,5- triazines, (the 3,5- dicyclohexyls-of 1,3,5- tri- 4- hydroxybenzyls) isocyanuric acid ester；

1.11. acyl amino phenol：4- hydroxylauranilides, 4- hydroxystearanilides, N- (bis- tertiary fourths of 3,5- Base -4- hydroxy phenyls)-carbamic acid octyl ester；

1.12. the ester of β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyls) propionic acid and following alcohol：Polyalcohol such as 1,6- oneself two Alcohol, 1,9- nonanediols, ethylene glycol, 1,2- propylene glycol, neopentyl glycol, Thiodiglycol, diethylene glycol (DEG), triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid ester, N, bis- (ethoxy) Oxalic acid diamides of N'-, 3- thiaundecanols, 3- thiapentadeca piols, three Methyl hexylene glycol, trimethylolpropane, 4- methylols -1- phospha -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane；

1.13. β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid, γ-(3,5- dicyclohexyl -4- hydroxy phenyls) third The ester of acid, 3,5- di-tert-butyl-hydroxy phenyls acetic acid and following alcohol：Unitary or polyalcohol such as methanol, ethyl alcohol, n-octyl alcohol, different Octanol, octadecanol, 1,6-HD, 1,9- nonanediols, ethylene glycol, 1,2- propylene glycol, neopentyl glycol, Thiodiglycol, two Glycol, triethylene glycol, pentaerythrite, three (ethoxy) isocyanuric acid esters, N, N'- double hydroxyethyls Oxalic acid diamides, 3- thio 11 Alkanol, 3- thiapentadeca piols, trimethyl hexylene glycol, trimethylolpropane, 4- methylol -1- phospha -2,6,7- trioxas are double Ring [2.2.2] octane；

1.14. the amide of β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid：Bis- (3,5- di-t-butyl -4- the hydroxyls of N, N'- Base phenylpropionyl) hexamethylene diamine, N, bis- (the 3,5- di-tert-butyl-hydroxy phenyls propiono) trimethylene diamines of N'-, Bis- (the 3,5- di-tert-butyl-hydroxy phenyls propiono) hydrazines of N, N'-；

1.15. ascorbic acid (vitamin C)；

1.16. amine antioxidants：N, N'- diisopropyl p-phenylenediamine, N,N' di sec butyl p phenylene diamine, N, N'- are bis- (1,4- dimethyl amyl groups) p-phenylenediamine, N, N- (1- ethyl -3- methyl amyls) p-phenylenediamine, N, N'- bis- (1- methylheptyls) - P-phenylenediamine, N, N'- dicyclohexyls p-phenylenediamine, N, N'- diphenyl-para-phenylene diamines, N, N'- bis- (naphthalene -2- bases)-p-phenylenediamine, N- isopropyl-N'- phenyl-pphenylenediamines, N- (1,3- dimethylbutyls)-N'- phenyl-pphenylenediamines, N- (1- methylheptyls)- N'- phenyl-pphenylenediamines, N- cyclohexyl-N'- phenyl-pphenylenediamines, 4- (tolysulfonyl amino)-diphenylamines, N, N'- bis- Methyl-N,N' di sec butyl p phenylene diamine, diphenylamines, N- allyls diphenylamines, 4- isopropoxydiphenylamines, 4- normal-butyl ammonia It is base phenol, 4- acylamino phenols, 4- nonanoyl aminophenols, 4- dodecanoylaminos phenol, 4- stearyls amino-phenol, double (4- methoxyphenyls) amine, 2,6- di-t-butyl -4- dimethylaminomethyls phenol, 2,4'- diaminodiphenyl-methanes, 4, 4'- diaminodiphenyl-methanes, N, N, N', N'- tetramethyl -4,4'- diaminodiphenylmethane, 1,2- bis- [(2- aminomethyl phenyls) Amino] ethane, 1,2- bis- (phenyl amino) propane, (o-tolyl) biguanides, two [4- (1', 3'- dimethylbutyl) phenyl] amine, Mixture, list and the dialkylation of t-octyl N- phenyl-1-naphthylamines, list and dialkylation tertiary butyl/t-octyl diphenylamine The mixture of nonyl diphenylamine, the mixture of list and dialkylation dodecyl diphenyl amine, list and dialkylation isopropyl/ The mixture of isohesyl diphenylamine, the mixture of list and dialkylation tert-butyl diphenyl amine, 2,3- dihydro -3,3- diformazans Mixture, list and the dialkyl group of base -4H-1,4- benzothiazines, phenthazine, list and dialkylation tertiary butyl/t-octyl-phenthazine Change mixture, N- allyls phenthazine, the N, N, N' of t-octyl phenthazine, N'- tetraphenyl -1,4- diamino but-2-ene, N, N- Bis- (2,2,6,6- tetramethyls-piperidin-4-yl) hexamethylene diamines, bis- (2,2,6,6- tetramethyl piperidine -4- bases) sebacates, 2,2,6,6- tetramethyl piperidine -4- ketone, 2,2,6,6- tetramethyl piperidine -4- alcohol.

2. the example of other antioxidants：Aliphatic series or aromatic phosphite, thio-2 acid or thiodiglycolic acid ester or Salt, the 2,2,12,12- tetramethyl -5,9- dihydroxy -3,7,11- trithio amido decane of aminodithioformic acid (thiamidecane) and 2,2,15,15- tetramethyl -5,12- dihydroxy -3,7,10,14- tetrathio hexadecanes.

3. the example of matal deactivator.Such as copper：

3.1. benzotriazole and its derivative：2- sulfhydryl benzotriazoles, 2,5- dimercaptos benzotriazole, 4- or 5- alkylbenzenes And triazole (such as tolytriazole (tolutriazole)) and its derivative, 4,5,6,7- tetrahydro benzos triazole, 5,5'- methylene Double benzotriazole；The Mannich base of benzotriazole or tolytriazole such as 1- [two (2- ethylhexyls) amino methyls] tolytriazoles and 1- [two (2- ethylhexyls) amino methyls] benzotriazole；Alkoxyalkyl benzotriazole such as (1- nonyl epoxides-methyl) benzo three Azoles, 1- (1- butoxyethyl groups)-benzotriazole and 1- (1- cyclohexyloxybu-tyls)-tolytriazole；

3.2. 1,2,4- triazoles and its derivative：The Manny of 3- alkyl-(or-aryl) 1,2,4- triazoles, 1,2,4- triazoles Uncommon alkali such as 1- [two (2- ethylhexyls) amino methyls] -1,2,4- triazoles；Alkoxyalkyl -1,2,4- triazoles such as 1- (1- fourth oxygen Base ethyl) -1,2,4- triazoles；Acylated 3- amino -1,2,4- triazoles；

3.3. imdazole derivatives：4,4'- methylene-bis- (2- undecyl -5- methyl) imidazoles and bis- [(N- methyl) miaows Azoles -2- bases] carbinol-octyl ether；

3.4. sulfur heterocyclic compound：2-mercaptobenzothiazole, 2,5- dimercapto -1,3,4- thiadiazoles, 2,5- dimercaptos Diazosulfide and its derivative；Bis- [two (2- ethylhexyls) amino methyls] -1,3,4- Thiadiazoline -2- ketone of 3,5-；

3.5. amino-compound：Salicylidene trimethylene diamine, salicylaminoguanidine and its salt.

4. the example of antirust agent：

4.1. organic acid, their ester, metal salt, amine salt and acid anhydrides：Alkyl and alkenyl succinic and its with alcohol, glycol Or the partial ester of hydroxycarboxylic acid, the inclined amide of alkyl and alkenyl succinic, 4- nonylphenoxyacetic acids, alkoxy-and alkoxy Ethyoxyl-carboxylic acid such as dodecyloxy acetic acid, dodecyloxy (ethyoxyl) acetic acid and its amine salt and KORANTIN SH take off Water sorbitol monooleate, lead naphthenate, alkenyl succinic anhydrides such as dodecenyl succinic anhydride, 2- (2- carboxyethyls)- 1- dodecyl -3- methylglycerins and its salt (especially its sodium salt and triethanolamine salt).

4.2. nitrogenous compound：

4.2.1. organic and inorganic acid uncle's aliphatic series or cycloaliphatic amines and amine salt, such as oil-soluble alkylammonium carboxylates and 1- [bis- (2- ethoxys) amino of N, N-] -3- (4- Nonylphenoxies) propan-2-ol；

4.2.2. heterocyclic compound：Substituted imidazoline andOxazoline such as 2- heptadecenes base -1- (2- ethoxys)-miaow Oxazoline；

4.2.3. sulfur-containing compound：Dinonyl naphthalene sulfonate barium, calcium mahogany sulfonate, the aliphatic carboxylic acid of alkylthio group substitution, aliphatic series The ester and its salt of 2- sulfo group carboxylic acids.

5. the example of additional viscosity index reinforcing agent：Polyacrylate, polymethacrylates, nitrogenous polymethylacrylic acid Methyl esters, vinyl pyrrolidone/methacrylate copolymer, polyvinylpyrrolidone, polybutene, polyisobutene, alkene are total Polymers such as ethylene-propylene copolymer, styrene-isoprene copolymer, hydration styrene-isoprene copolymer, styrene/ Acrylate copolymer and polyethers.Also the multi-functional viscosity improver with dispersant and/or antioxidant properties is known, And it can also optionally be used other than product of the present invention.

6. the example of pour-point depressant：Polymethacrylates, ethylene/vinyl acetate, alkyl polystyrene, Fumarate copolymer, alkylated naphthalene derivative.

7. the example of dispersant：Polybutenyl succinic acid amide or acid imide, polybutylene-based phosphonic acids derive The sulfonate and phenates of object, alkaline magnesium, calcium and barium.

8. the example of extreme pressure and antiwear additive：The compound of sulfur-bearing and halogen such as chlorinated paraffin, olefine sulfide or plant Oily (soybean oil, rape oil), alkyl or aryl two or trisulfide, benzotriazole or derivatives thereof are such as bis- (2- ethylhexyls) amino Methyl toluene triazole, dithiocarbamate such as di-2-ethylhexylphosphine oxide Keywords dibutyl dithiocarbamate, 2- sulfhydryl benzotriazoles Derivative such as 1- [bis- (2- ethylhexyls) amino methyls of N, N-] -2- sulfydryl -1H-1,3- benzothiazoles, dimercapto -1 2,5-, Bis- (tertiary nonyl two the is thio) -1,3,4- thiadiazoles of the derivative of 3,4- thiadiazoles such as 2,5-.

9. the example of friction coefficient depressant：Lard, oleic acid, tallow, rape oil, sulfurized fatty, amide, amine.EP-A-0 Other examples are given in 565 487.

10. the example for water/oil metal working fluids and the special additive of hydraulic fluid：Emulsifier：Mahogany acid Salt, amine such as polyoxyethylated fatty amines, non-ionic surface active substance；Buffer：Such as alkanolamine；Biocide：Triazine, thiophene Oxazoline ketone, nitroform, morpholine, mercaptopyridine sodium；Process velocity modifier：Sulfoacid calcium and barium.

Poly- (methyl) acrylate copolymer of the present invention can be used as the viscosity index improver in lubricant oil composite, and can It is mixed with base oil and at least one above-mentioned additive to form required lubricant oil composite.It can also prepare first comprising required Then the concentrate or so-called " additive packet " of additive spectrum can make its dilution to obtain the work of expected lubricant oil composite Make concentration.

Including the lubricant oil composite of poly- (methyl) acrylate copolymer of the present invention can be used for many different applications, wrap Include automatic transmission fluids, manual transmission fluid, hydraulic fluid, lubricating grease, gear fluids, metal working fluids, crankcase Engine oil is applied and/or shock absorber fluids.

Poly- (methyl) acrylate copolymer of the present invention can be used for preparing the lubricating oil group with particular technology performance characteristic Close object.

Most significantly, the rheological curve of lubricant oil composite of the present invention at low temperatures and high temperatures (is included in wide temperature range The temperature dependency of interior kinematic viscosity) be it is excellent, such as can by under different temperatures measure kinematic viscosity, viscosity index (VI) and it is cold Dynamic simulator (CCS) test obtains.

Further it should be noted that the shear stability of lubricant oil composite of the present invention is also very good simultaneously, such as shear steady Overall qualitative index and commonly used in characterize lubricating oil shear stability other technological parameters as at elevated temperatures (such as At 100 DEG C or 150 DEG C) high temperature high shear (HTHS) viscosity indicated by.

In short, the combination of the temperature dependent viscosity curve and high shear stability of lubricant oil composite of the present invention is shown The uncommon performance characteristic of lubricant oil composite is composed, because these effects usually to having adverse effect each other.

Poly- (methyl) acrylate copolymer also has the advantages that other, i.e. the anti-oxidant additives needs of decrement include Finally to have good oxidation stability in lubricant oil composite of the present invention.

Therefore, lubricant oil composite of the present invention usually can even improve the fuel economy of engine.

The invention further relates to a kind of methods for improving the shear stability of lubricant oil composite, wherein the method packet Poly- (methyl) acrylate copolymer of the offer present invention is provided and is added into base oil and optional additive and is changed with being formed to have Into shear stability lubricant oil composite the step of.

Embodiment

1. method

According to DIN 55672-1, the relative weight average molecule of polymer is measured based on gpc measurement using polystyrene standards Amount and molecular weight distribution.

The kinematic viscosity at 100 DEG C is measured according to ASTM D445.

The high-temperature high shear viscosity (HTHS) at 100 DEG C and 150 DEG C respectively is measured according to ASTM D5481.

Viscosity index (VI) (VI) is measured according to ASTM D2270.

Based on the shear stability index (SSI) measured according to ASTM D7109 (30 logical journeys) and pass through ASTM method D6022 calculates shear stability index (SSI) to measure shear stability.

2. the polymerization of methacrylate

By the 54g degrees of branching for 3.1 the branched C17 Arrcostabs (C17MA) of methacrylic acid (such as institute in WO 09/124979A1 State preparation and measurement), 45g methyl methacrylates (MMA), 81g methacrylic acid straight chain stearyls (SMA) and 242mg ten Dialkyl group mercaptan is (as 10%3030 solution) in 1 liter of four-neck flask in 325g from Neste Oil'sIt is mixed in 3030 base oils.95 DEG C are heated the mixture to, colorless cleared solution is obtained.It is excessively pungent to prepare 0.13g Solution of the tert-butyl acrylate in 6g Nexbase 3030, and be continually fed into flask with the rate of 0.0413ml/min.It is small 3 Shi Hou, by Isosorbide-5-Nitrae 86ml, the solution is fed in product mixtures in 30 minutes.Obtained polymer solution is not being had any other It is stirred 90 minutes at 95 DEG C under initiator feed.So that solution is cooled to room temperature and forms colourless viscous liquid.

Using Brookfield viscometer 557.3mm is measured at 100 DEG C (KV100)²The kinematic viscosity of/s (cSt).

Gpc analysis (polystyrene standards)：Detector：DRI Agilent 1100 UV Agilent 1100 VWD [254nm], eluent：+ 0.1% trifluoroacetic acid eluent of tetrahydrofuran, flow velocity：1ml/min), concentration：2mg/ml, column： PLgel MIXED-B

M_n=128000g/mol, M_w=384000g/mol, PDI=3.0；

The produced above polymer for including C17MA, MMA and SMA, with different C17MA and SMA contents, excessively sad The amount of the tert-butyl ester and lauryl mercaptan.Reaction temperature, solvent and polymer concentration are kept constant.It measures molten at 100 DEG C The viscosity (KV100) of liquid, and pass through gpc analysis polymer.The characteristic of resulting polymers is summarised in Tables 1 and 2.

Table 1：

*=except the scope of the present invention

Table 2：

3. the preparation of machine oil blend

Lubricant oil composite B1-B7 is obtained using copolymer p 1-P7 produced above.

As the base oil component in lubricant oil composite B1-B7, Group III base oil is added.As other commercially available purchases Car engine oils additive includes packaging Infineum V 534.

The amount of each component is as follows in blend B1-B7：

Copolymer p 1-P7：3.5-5.0 weight %

Base oil component：81.9-83.4 weight %

Additive：13.1 weight %

Measure the rheological behaviour and other performance characteristics of lubricant oil composite B1-B7.Table 3 shows C17MA in PMA polymer The increase of content makes SSI reduce, and improves the shear stability of polymer and corresponding preparaton.The display of table 4 has higher The polymer of C17MA contents and suitable molecular weight leads to higher VI in oily preparaton.

Table 3：

*=except the scope of the present invention

Table 4：

4. the polymerization for 20 methacrylates of Guerbet that the degree of branching is 1：

By the 135g degrees of branching be 1 the branched C20 Arrcostabs (C20MA) of methacrylic acid, 45g methyl methacrylate (MMA) and 60mg lauryl mercaptans (as 3030 solution of 10%Nexbase) come from Neste in 1 liter of four-neck flask in 325g It is mixed in 3030 base oils of Nexbase of Oil.95 DEG C are heated the mixture to, colorless cleared solution is obtained.Prepare 0.13g mistakes Solution of the octanoic acid ter-butyl ester in 6g Nexbase 3030, and be continually fed into flask with the rate of 0.0413ml/min.3 After hour, by Isosorbide-5-Nitrae 86ml, the solution is fed in product mixtures in 30 minutes.Then obtained polymer solution is not being appointed It is stirred 90 minutes at 95 DEG C what under his initiator feed.So that solution is cooled to room temperature and forms colourless viscous liquid.

Using Brookfield viscometer, (KV100) measures 659mm at 100 DEG C²The kinematic viscosity of/s (cSt).

M_n=109000g/mol, M_w=446000g/mol, PDI=4.1；

The preparation of machine oil blend

By copolymer for obtaining lubricant oil composite.

As basic oil ingredient, Group III base oil is added.Include packaging as other commercially available car engine oils additives Infineum V 534。

Measure the shear stability of blend.Obtain 51 SSI.

With the degree of branching be 3.1 embodiment 2 polymer engine oil blend compared with, it can be seen that the degree of branching 1 Polymer shear stability index (last column of table 3) notable higher.

The higher degree of branching causes SSI to reduce, this is related with the increase of shear stability.

Claims

1. a kind of poly- (methyl) acrylate copolymer can be obtained by polymerizeing the mixture comprising following substance：

(A) (methyl) acrylic acid C17 Arrcostabs, wherein C17 alkyl chains are branched with the average branchiness of 2.0-4.0,

(B) methyl methacrylate and/or methyl acrylate, and

(C) alkyl methacrylate and/or alkyl acrylate with straight chain or branched C2-C30 alkyl chains.

2. the copolymer of claim 1, wherein C17 alkyl chains are branched with the average branchiness of 2.8-3.7.

It is surveyed by gel permeation chromatography according to DIN 55672-1 3. the copolymer of claims 1 or 2, wherein copolymer have The weight average molecular weight M of fixed 10,000-800,000_W。

4. the copolymer of claim 1-3, wherein the total weight based on poly- (methyl) acrylate copolymer, comonomer (A) Amount be 5-80 weight %.

5. the copolymer of claim 1-4, wherein the total weight based on poly- (methyl) acrylate copolymer, comonomer (B) Amount be 5-40 weight %.

6. the copolymer of claim 1-5, wherein the total weight based on poly- (methyl) acrylate copolymer, comonomer (C) Amount be 15-80 weight %.

7. the copolymer of claim 1-6, wherein straight chain or branched C2-C30 alkyl chains are selected from ethyl, n-propyl, isopropyl, just Butyl, isobutyl group, sec-butyl, tertiary butyl, amyl, hexyl, heptyl, octyl, 2- ethylhexyls, 2- propylheptyls, nonyl, the last of the ten Heavenly stems Base, stearyl, lauryl, octadecyl, heptadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, two Tridecyl, tetracosyl, pentacosyl, cerul, cerul, octacosyl, nonacosyl, three Ten alkyl and mountainBase.

8. a kind of concentrate composition in lubricating oil, it includes：

(i) diluent, and

(ii) poly- (methyl) acrylate copolymer according to claim 1-7 of 30-70 weight %.

9. a kind of lubricant oil composite, it includes：

(a) base oil,

(b) according to poly- (methyl) acrylate copolymer of claim 1-7, and

(c) additive.

10. the lubricant oil composite of claim 8, it includes

Poly- (methyl) acrylate copolymer according to claim 1-7 of 0.1-30 weight %,

The base oil of 70-99.9 weight %, and

The additive of 0.05-20 weight %.

11. the lubricant oil composite of claim 9 or 10, wherein additive include at least one selected from antioxidant, oxidation suppression Under preparation, corrosion inhibitor, friction modifiers, matal deactivator, antirust agent, antifoaming agent, viscosity index (VI) reinforcing agent, additional pour point The additive of depressant prescription, dispersant, detergent, other extreme pressure agents and antiwear additive.

12. the lubricant oil composite of claim 9-11 has and is measured according to ASTM D7109 and calculated by ASTM D6022 Be less than 50 shear stability index.

13. the lubricant oil composite of claim 9-12 has and measures the 100 of 4.00-6.00mPas according to ASTM D5481 High-temperature high shear viscosity at DEG C.

14. the lubricant oil composite of claim 9-13 is in automatic transmission fluids, manual transmission fluid, hydraulic fluid, profit Purposes in consistent lubricant, gear fluids, metal working fluids, crankcase engine oil or shock absorber fluids.

15. a kind of method for improving lubricating oil shear stability, wherein the method includes will be according to claim 1-7's Poly- (methyl) acrylate copolymer is added in the lubricant oil composite comprising base oil and additive.